JP5377925B2 - Lubricating oil composition for internal combustion engines - Google Patents
Lubricating oil composition for internal combustion engines Download PDFInfo
- Publication number
- JP5377925B2 JP5377925B2 JP2008272188A JP2008272188A JP5377925B2 JP 5377925 B2 JP5377925 B2 JP 5377925B2 JP 2008272188 A JP2008272188 A JP 2008272188A JP 2008272188 A JP2008272188 A JP 2008272188A JP 5377925 B2 JP5377925 B2 JP 5377925B2
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- JP
- Japan
- Prior art keywords
- mass
- composition
- alkenyl
- lubricating oil
- internal combustion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 81
- 239000010687 lubricating oil Substances 0.000 title claims description 45
- 238000002485 combustion reaction Methods 0.000 title claims description 35
- -1 alkyl succinimide Chemical compound 0.000 claims description 76
- 239000002199 base oil Substances 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 125000003342 alkenyl group Chemical group 0.000 claims description 32
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 27
- 229910052796 boron Inorganic materials 0.000 claims description 21
- 229960002317 succinimide Drugs 0.000 claims description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000001384 succinic acid Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 33
- 229910052751 metal Inorganic materials 0.000 description 23
- 125000000217 alkyl group Chemical group 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- 229910052717 sulfur Inorganic materials 0.000 description 19
- 229920001973 fluoroelastomer Polymers 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000003921 oil Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 239000011593 sulfur Substances 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 230000003749 cleanliness Effects 0.000 description 14
- 239000003599 detergent Substances 0.000 description 14
- 230000003078 antioxidant effect Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 150000001342 alkaline earth metals Chemical class 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- 235000010446 mineral oil Nutrition 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 159000000007 calcium salts Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 5
- 239000006078 metal deactivator Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229940014800 succinic anhydride Drugs 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 229960001860 salicylate Drugs 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JDVPQXZIJDEHAN-UHFFFAOYSA-N succinamic acid Chemical compound NC(=O)CCC(O)=O JDVPQXZIJDEHAN-UHFFFAOYSA-N 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 2
- SZOLUXDHHKCYKT-ONEGZZNKSA-N (e)-but-1-en-1-amine Chemical compound CC\C=C\N SZOLUXDHHKCYKT-ONEGZZNKSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
- QHPKIUDQDCWRKO-UHFFFAOYSA-N 2,6-ditert-butyl-4-[2-(3,5-ditert-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 QHPKIUDQDCWRKO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NWPCFCBFUXXJIE-UHFFFAOYSA-N 2-(hydroxymethylamino)ethanol Chemical compound OCCNCO NWPCFCBFUXXJIE-UHFFFAOYSA-N 0.000 description 1
- XQESJWNDTICJHW-UHFFFAOYSA-N 2-[(2-hydroxy-5-methyl-3-nonylphenyl)methyl]-4-methyl-6-nonylphenol Chemical compound CCCCCCCCCC1=CC(C)=CC(CC=2C(=C(CCCCCCCCC)C=C(C)C=2)O)=C1O XQESJWNDTICJHW-UHFFFAOYSA-N 0.000 description 1
- IJPXXOVHDMEUSR-UHFFFAOYSA-N 2-[2-hydroxyethyl(undecyl)amino]ethanol Chemical compound CCCCCCCCCCCN(CCO)CCO IJPXXOVHDMEUSR-UHFFFAOYSA-N 0.000 description 1
- BITAPBDLHJQAID-KTKRTIGZSA-N 2-[2-hydroxyethyl-[(z)-octadec-9-enyl]amino]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCCN(CCO)CCO BITAPBDLHJQAID-KTKRTIGZSA-N 0.000 description 1
- GTLMTHAWEBRMGI-UHFFFAOYSA-N 2-cyclohexyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C2CCCCC2)=C1 GTLMTHAWEBRMGI-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- BGWNOSDEHSHFFI-UHFFFAOYSA-N 2-tert-butyl-4-[(3-tert-butyl-4-hydroxy-5-methylphenyl)methylsulfanylmethyl]-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CSCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 BGWNOSDEHSHFFI-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- TVDZNGHKRSKPCD-UHFFFAOYSA-N 4-heptyl-n-(4-heptylphenyl)aniline Chemical compound C1=CC(CCCCCCC)=CC=C1NC1=CC=C(CCCCCCC)C=C1 TVDZNGHKRSKPCD-UHFFFAOYSA-N 0.000 description 1
- SOASHAVJCWKTKL-UHFFFAOYSA-N 4-methyl-2,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C)=CC(C(C)(C)CC)=C1O SOASHAVJCWKTKL-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- FCQAFXHLHBGGSK-UHFFFAOYSA-N 4-nonyl-n-(4-nonylphenyl)aniline Chemical compound C1=CC(CCCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCCC)C=C1 FCQAFXHLHBGGSK-UHFFFAOYSA-N 0.000 description 1
- JBHUAGYANLGUJR-UHFFFAOYSA-N B(O)(O)O.C(CCC(=O)O)(O)=N Chemical compound B(O)(O)O.C(CCC(=O)O)(O)=N JBHUAGYANLGUJR-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- ZZGHZLUTIKGEDL-UHFFFAOYSA-M C(CC(C)C)SP(=S)(OCCC(C)C)[O-].[Zn+] Chemical compound C(CC(C)C)SP(=S)(OCCC(C)C)[O-].[Zn+] ZZGHZLUTIKGEDL-UHFFFAOYSA-M 0.000 description 1
- DWLMIYNUGWGKQW-UHFFFAOYSA-N C(CCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCC)CCCC)CCCC Chemical compound C(CCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCC)CCCC)CCCC DWLMIYNUGWGKQW-UHFFFAOYSA-N 0.000 description 1
- WFHKDFKMMXNXBE-UHFFFAOYSA-N C(CCCCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCCCC)CCCCCC)CCCCCC Chemical compound C(CCCCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCCCC)CCCCCC)CCCCCC WFHKDFKMMXNXBE-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
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- NCEGDHPVRKYIJN-UHFFFAOYSA-N n-pentyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCC)C1=CC=CC=C1 NCEGDHPVRKYIJN-UHFFFAOYSA-N 0.000 description 1
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- 231100000989 no adverse effect Toxicity 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
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- 229920001083 polybutene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
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- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000013099 sulfated ash test Methods 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- WAILXPVSJYWOEV-UHFFFAOYSA-L zinc;(2,3-didodecylphenyl)sulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCCCCC1=CC=CC(SP([O-])([O-])=S)=C1CCCCCCCCCCCC WAILXPVSJYWOEV-UHFFFAOYSA-L 0.000 description 1
- OBPRGCGYBYCAIB-UHFFFAOYSA-L zinc;(2,3-dipentylphenyl)sulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCC1=CC=CC(SP([O-])([O-])=S)=C1CCCCC OBPRGCGYBYCAIB-UHFFFAOYSA-L 0.000 description 1
- NDMGGNOLFUKCSA-UHFFFAOYSA-L zinc;(2,3-dipropylphenyl)sulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCC1=CC=CC(SP([O-])([O-])=S)=C1CCC NDMGGNOLFUKCSA-UHFFFAOYSA-L 0.000 description 1
- DAIDCNOEIKGXQG-UHFFFAOYSA-L zinc;(2-methyl-3,4-dipropylphenyl)sulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCC1=CC=C(SP([O-])([O-])=S)C(C)=C1CCC DAIDCNOEIKGXQG-UHFFFAOYSA-L 0.000 description 1
- PXJZGBFRKRTOPA-UHFFFAOYSA-L zinc;[2,3-di(nonyl)phenyl]sulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCC1=CC=CC(SP([O-])([O-])=S)=C1CCCCCCCCC PXJZGBFRKRTOPA-UHFFFAOYSA-L 0.000 description 1
- ZNCAMSISVWKWHL-UHFFFAOYSA-L zinc;butoxy-butylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCOP([O-])(=S)SCCCC.CCCCOP([O-])(=S)SCCCC ZNCAMSISVWKWHL-UHFFFAOYSA-L 0.000 description 1
- BCLLIVNRSGTXBX-UHFFFAOYSA-L zinc;decoxy-decylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCCOP([O-])(=S)SCCCCCCCCCC.CCCCCCCCCCOP([O-])(=S)SCCCCCCCCCC BCLLIVNRSGTXBX-UHFFFAOYSA-L 0.000 description 1
- ZBDJNBFTEIUHPK-UHFFFAOYSA-L zinc;dihexoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCOP([S-])(=S)OCCCCCC.CCCCCCOP([S-])(=S)OCCCCCC ZBDJNBFTEIUHPK-UHFFFAOYSA-L 0.000 description 1
- VYEHCXHIPZIYIJ-UHFFFAOYSA-L zinc;dodecoxy-dodecylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCCCCOP([O-])(=S)SCCCCCCCCCCCC.CCCCCCCCCCCCOP([O-])(=S)SCCCCCCCCCCCC VYEHCXHIPZIYIJ-UHFFFAOYSA-L 0.000 description 1
- GBEDXBRGRSPHRI-UHFFFAOYSA-L zinc;octoxy-octylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCOP([O-])(=S)SCCCCCCCC.CCCCCCCCOP([O-])(=S)SCCCCCCCC GBEDXBRGRSPHRI-UHFFFAOYSA-L 0.000 description 1
- HHMFJIHYTYQNJP-UHFFFAOYSA-L zinc;oxido-pentoxy-pentylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCOP([O-])(=S)SCCCCC.CCCCCOP([O-])(=S)SCCCCC HHMFJIHYTYQNJP-UHFFFAOYSA-L 0.000 description 1
- LZVDFWITYZHIEU-UHFFFAOYSA-L zinc;oxido-propoxy-propylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCOP([O-])(=S)SCCC.CCCOP([O-])(=S)SCCC LZVDFWITYZHIEU-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Lubricants (AREA)
Description
本発明は、ディーゼルエンジンやガソリンエンジン等に使用される内燃機関用潤滑油組成物に関する。 The present invention relates to a lubricating oil composition for internal combustion engines used in diesel engines, gasoline engines, and the like.
現在、地球規模での環境規制はますます厳しくなり、自動車を取り巻く状況も、燃費規制、排出ガス規制等厳しくなる一方である。この背景には地球温暖化等の環境問題と、石油資源の枯渇に対する懸念からの資源保護がある。以上の理由から自動車の省燃費化はますます進められると考えられる。
自動車の省燃費化を図るためには、自動車の軽量化、エンジンの改良等、自動車自体の改良だけでなく、エンジンにおける摩擦ロスを防ぐためのエンジン油の低粘度化、良好な摩擦調整剤の添加等、エンジン油自体の改良が極めて重要である。また、ディーゼルエンジンにおいては、パティキュレート・マター（ＰＭ）およびＮＯｘなどの排出ガス成分による環境汚染を軽減するための対策が重要な課題となっている。その対策としては、自動車にパティキュレート・フィルターや排出ガス浄化触媒（酸化または還元触媒）などの排出ガス浄化装置を装着することが有力である。一方、そのような排出ガス浄化装置を装着した自動車に従来の内燃機関用潤滑油を用いた場合、パティキュレート・フィルターに付着した煤は酸化、燃焼により取り除かれるものの、燃焼により生成した金属酸化物や、リン酸塩、硫酸塩、カルボン酸塩などによってフィルタが目詰まりするという問題が生じている。また、使用されたエンジン油の一部は燃焼し、排出ガスとして排出される。従って、潤滑油中の金属分や硫黄分もできるだけ少ない方が好ましい。さらに、触媒の劣化を防ぐためには、潤滑油中のリン分および硫黄分も減らすことも重要である。
Currently, environmental regulations on a global scale are becoming stricter, and the situation surrounding automobiles is becoming stricter, such as fuel efficiency regulations and exhaust gas regulations. This is due to environmental issues such as global warming and resource protection from concerns over the depletion of petroleum resources. For these reasons, it is considered that the fuel saving of automobiles will be promoted more and more.
In order to reduce the fuel consumption of automobiles, not only the improvement of the automobile itself, such as the weight reduction of the automobile and the improvement of the engine, but also the low viscosity of the engine oil to prevent friction loss in the engine, Improvement of engine oil itself, such as addition, is extremely important. In diesel engines, measures for reducing environmental pollution caused by exhaust gas components such as particulate matter (PM) and NOx are important issues. As a countermeasure, it is effective to mount an exhaust gas purification device such as a particulate filter or an exhaust gas purification catalyst (oxidation or reduction catalyst) on the automobile. On the other hand, when a conventional lubricating oil for an internal combustion engine is used in an automobile equipped with such an exhaust gas purification device, the soot adhering to the particulate filter is removed by oxidation and combustion, but the metal oxide generated by combustion In addition, there is a problem that the filter is clogged by phosphate, sulfate, carboxylate, or the like. A part of the used engine oil is burned and discharged as exhaust gas. Therefore, it is preferable that the metal content and sulfur content in the lubricating oil be as small as possible. Furthermore, in order to prevent catalyst deterioration, it is also important to reduce the phosphorus and sulfur contents in the lubricating oil.
そこで、潤滑油基油に対して、所定のモリブデンジチオカルバメート、ジアルキルジチオリン酸亜鉛、およびホウ素含有コハク酸イミドを配合し、モリブデンジチオカルバメートに由来するモリブデンの量と、ジアルキルジチオリン酸亜鉛に由来するリンの量、および、ホウ素含有コハク酸イミドに由来するホウ素の量を規定した潤滑油組成物が提案されている（例えば、特許文献１参照）。特許文献１の潤滑油組成物によれば、特に中低温かつ低速運転下で低摩擦係数を与える旨の記載がある（明細書段落〔００１１〕）。
また、潤滑油基油に対し、所定のホウ素含有無灰分散剤、およびジチオリン酸亜鉛を配合し、組成物中のホウ素含有量と、ホウ素含有量／リン含有量比を規定して、硫酸灰分量が１．０質量％以下である潤滑油組成物が提案されている（例えば、特許文献２参照）。特許文献２の潤滑油組成物によれば、高温清浄性に優れるとともに、低灰分でパティキュレートトラップや排ガス浄化装置への悪影響もない旨が記載されている（明細書段落〔００３５〕）。
さらに、潤滑油基油に、所定のコハク酸イミド、そのホウ素誘導体、および所定の酸化防止剤を配合し、硫酸灰分を１．２質量％以下とした潤滑油組成物が提案されている（例えば、特許文献３参照）。特許文献３の潤滑油組成物によれば、低灰分量でありながら酸化安定性に優れる内燃機関用潤滑油組成物を提供できる旨の記載がある（明細書段落〔０００８〕）。
Therefore, a predetermined molybdenum dithiocarbamate, zinc dialkyldithiophosphate, and boron-containing succinimide are blended with the lubricating base oil, and the amount of molybdenum derived from molybdenum dithiocarbamate and phosphorus derived from zinc dialkyldithiophosphate. And a lubricating oil composition in which the amount of boron derived from boron-containing succinimide is defined (see, for example, Patent Document 1). According to the lubricating oil composition of Patent Document 1, there is a description that a low coefficient of friction is given particularly under medium and low temperature and low speed operation (paragraph [0011] in the specification).
In addition, a predetermined boron-containing ashless dispersant and zinc dithiophosphate are blended with the lubricating base oil, the boron content in the composition and the boron content / phosphorus content ratio are defined, and the sulfated ash content Has been proposed (see, for example, Patent Document 2). According to the lubricating oil composition of Patent Document 2, it is described that it is excellent in high-temperature cleanability and has a low ash content and has no adverse effect on the particulate trap and the exhaust gas purification device (paragraph [0035] of the specification).
Furthermore, a lubricating oil composition in which a predetermined succinimide, a boron derivative thereof, and a predetermined antioxidant are blended with a lubricating base oil to have a sulfated ash content of 1.2% by mass or less has been proposed (for example, And Patent Document 3). According to the lubricating oil composition of Patent Document 3, there is a description that a lubricating oil composition for an internal combustion engine having a low ash content and excellent oxidation stability can be provided (paragraph [0008] of the specification).
一方、内燃機関においては、シール性、耐薬品性および耐熱性に優れるフッ素ゴムが各部分に多用されている。しかしながら、内燃機関の内部は高温となるため、潤滑油に触れたフッ素ゴムが劣化してクラックが発生し、シール寿命が短くなるという問題がある。これに対して、特許文献１〜３に記載の内燃機関用潤滑油組成物は、フッ素ゴムシールへの適合性が考慮されておらず、内燃機関内部で使用されるフッ素ゴムシールの寿命が長いとはいえない。
そこで、本発明は、ガソリンエンジンやディーゼルエンジンなどの内燃機関に用いた場合に、高温清浄性に優れるとともに、内燃機関内部に使用されるフッ素ゴムシールへの適合性が良好な内燃機関用潤滑油組成物を提供することを目的とする。
On the other hand, in an internal combustion engine, fluoro rubber having excellent sealing properties, chemical resistance, and heat resistance is frequently used in each part. However, since the internal temperature of the internal combustion engine becomes high, there is a problem that the fluororubber that has come into contact with the lubricating oil is deteriorated to cause cracks and shorten the seal life. On the other hand, the lubricating oil composition for internal combustion engines described in Patent Documents 1 to 3 does not consider compatibility with the fluororubber seal, and the life of the fluororubber seal used inside the internal combustion engine is long. I can't say that.
Therefore, the present invention provides a lubricating oil composition for an internal combustion engine that is excellent in high-temperature cleanliness when used in an internal combustion engine such as a gasoline engine or a diesel engine, and has good compatibility with a fluororubber seal used inside the internal combustion engine. The purpose is to provide goods.
前記課題を解決すべく、本発明は、以下のような内燃機関用潤滑油組成物を提供するものである。
［１］基油に、（Ａ）アルケニル若しくはアルキルコハク酸イミドおよびそのホウ素化物を配合してなる内燃機関用潤滑油組成物であって、前記（Ａ）成分は、（Ａ−１）アルケニル若しくはアルキルコハク酸モノイミド構造および（Ａ−２）アルケニル若しくはアルキルコハク酸ビスイミド構造を含み、前記（Ａ−１）構造に由来する窒素と、前記（Ａ−２）構造に由来する窒素との質量比（（Ａ−１）／（Ａ−２））が０．５以下であり、前記（Ａ）成分におけるアルケニル若しくはアルキルコハク酸イミドホウ素化物を構成するホウ素と窒素の質量比（Ｂ／Ｎ比）が０．５以上であり、前記（Ａ）成分におけるアルケニル若しくはアルキルコハク酸イミドホウ素化物に由来するホウ素含有量が組成物全量基準において０．０２〜０．０５質量％であり、さらに（Ｄ）成分として、多価アルコールモノ脂肪酸エステルのホウ素化物を配合してなることを特徴とする内燃機関用潤滑油組成物。
In order to solve the above problems, the present invention provides the following lubricating oil composition for an internal combustion engine.
[1] A lubricating oil composition for an internal combustion engine comprising (A) an alkenyl or alkyl succinimide and a borated product thereof in a base oil, wherein the component (A) includes (A-1) alkenyl or Mass ratio of nitrogen derived from the (A-1) structure and nitrogen derived from the (A-2) structure, including an alkyl succinic acid monoimide structure and (A-2) alkenyl or alkyl succinic acid bisimide structure ( (A-1) / (A-2)) is 0.5 or less, and the mass ratio (B / N ratio) of boron and nitrogen constituting the alkenyl or alkyl succinimide boride in the component (A) is as follows. The boron content derived from the alkenyl or alkyl succinimide boride in the component (A) is 0.5 to 0.0 on the basis of the total amount of the composition. Ri% by mass, further as the component (D), polyhydric alcohols internal combustion engine lubricating oil composition characterized by being obtained by blending the boron compound of the mono-fatty acid esters.
［２］［１］に記載の内燃機関用潤滑油組成物において、さらに、（Ｂ）モリブデンジチオカーバメートを、組成物全量基準におけるモリブデン量換算で０．０１〜０．０８質量％配合してなることを特徴とする内燃機関用潤滑油組成物。 [2] The lubricating oil composition for internal combustion engines according to [1], further comprising (B) molybdenum dithiocarbamate in an amount of 0.01 to 0.08% by mass in terms of molybdenum based on the total amount of the composition. A lubricating oil composition for an internal combustion engine.
［３］上述の［１］または［２］に記載の内燃機関用潤滑油組成物において、さらに、（Ｃ）ジアルキルジチオリン酸亜鉛を、組成物全量基準におけるリン量換算で０．０７〜０．０９質量％配合してなることを特徴とする内燃機関用潤滑油組成物。 [3] In the lubricating oil composition for internal combustion engines according to the above [1] or [2], (C) zinc dialkyldithiophosphate is further converted to 0.07 to 0.00 in terms of phosphorus based on the total amount of the composition. A lubricating oil composition for an internal combustion engine, characterized by comprising 09% by mass.
［４］上述の［１］から［３］までのいずれか一つに記載の内燃機関用潤滑油組成物において、前記（Ｄ）成分を０．１〜１質量％配合してなることを特徴とする内燃機関用潤滑油組成物。 [4] The internal combustion engine lubricating oil composition according to any one of [1] to [3] above , wherein 0.1 to 1% by mass of the component (D) is blended. A lubricating oil composition for an internal combustion engine.
［５］上述の［１］から［４］までのいずれか一つに記載の内燃機関用潤滑油組成物において、該組成物の硫酸灰分が０．６質量％以下であることを特徴とする内燃機関用潤滑油組成物。 [5] The lubricating oil composition for internal combustion engines according to any one of [1] to [4] above, wherein the sulfated ash content of the composition is 0.6% by mass or less. Lubricating oil composition for internal combustion engines.
本発明によれば、特定のアルケニル若しくはアルキルコハク酸イミドおよびそのホウ素化物を所定量配合しているので、低灰分量であっても高温清浄性に優れ、かつ内燃機関内部に使用されるフッ素ゴムシールへの適合性が良好な内燃機関用潤滑油組成物を提供できる。 According to the present invention, since a predetermined amount of a specific alkenyl or alkyl succinimide and a boride thereof are blended, the fluororubber seal is excellent in high temperature cleanliness even with a low ash content and used inside an internal combustion engine. It is possible to provide a lubricating oil composition for an internal combustion engine having good compatibility with the above.
本発明は、基油に特定の（Ａ）アルケニル若しくはアルキルコハク酸イミドおよびそのホウ素化物を配合してなる内燃機関用潤滑油組成物（以下、単に「本組成物」ともいう。）である。以下に、本発明の実施形態を詳細に説明する。 The present invention is a lubricating oil composition for internal combustion engines (hereinafter, also simply referred to as “the present composition”) obtained by blending a specific (A) alkenyl or alkyl succinimide and a borated product thereof into a base oil. Hereinafter, embodiments of the present invention will be described in detail.
〔基油〕
本組成物の基油としては、鉱油でも合成油でもよい。この鉱油や合成油の種類については特に制限はなく、従来、内燃機関用潤滑油の基油として使用されている鉱油や合成油の中から任意のものを適宜選択して用いることができる。
鉱油としては、例えば、原油を常圧蒸留して得られる常圧残油を減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製等の１つ以上の処理を行って精製した鉱油、あるいはワックス、ＧＴＬ ＷＡＸを異性化することによって製造される鉱油等が挙げられる。
また、合成油としては、例えば、ポリブテン、ポリオレフィン［α−オレフィン単独重合体や共重合体（例えばエチレン−α−オレフィン共重合体）など］、各種のエステル（例えば、ポリオールエステル、二塩基酸エステル、リン酸エステルなど），各種のエーテル（例えば、ポリフェニルエーテルなど）、ポリグリコール、アルキルベンゼン、アルキルナフタレンなどが挙げられる。これらの合成油のうち、粘度特性、添加剤の溶解性およびシールゴムへの適合性の観点より特にポリオレフィン、ポリオールエステルが好ましい。
本発明においては、基油として、上記鉱油を１種用いてもよく、２種以上を組み合わせて用いてもよい。また、上記合成油を１種用いてもよく、２種以上を組み合わせて用いてもよい。さらには、鉱油１種以上と合成油１種以上とを組み合わせて用いてもよい。
基油の粘度については特に制限はなく、潤滑油組成物の用途に応じて異なるが、１００℃の動粘度が３〜８ｍｍ２／ｓであることが好ましく、１００℃における動粘度が３ｍｍ２／ｓ以上であれば蒸発損失が少なく、一方８ｍｍ２／ｓ以下であれば、粘性抵抗による動力損失が小さく、燃費改善効果が得られる。
[Base oil]
The base oil of the composition may be mineral oil or synthetic oil. There is no restriction | limiting in particular about the kind of this mineral oil or synthetic oil, Arbitrary things can be suitably selected and used from the mineral oil and synthetic oil conventionally used as a base oil of the lubricating oil for internal combustion engines.
As mineral oil, for example, a lubricating oil fraction obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil can be desolvated, solvent extracted, hydrocracked, solvent dewaxed, catalytic dehydrated. Mineral oil refined by one or more treatments such as wax, hydrorefining, or the like, or mineral oil produced by isomerizing wax, GTL WAX, and the like.
Synthetic oils include, for example, polybutene, polyolefins [α-olefin homopolymers and copolymers (for example, ethylene-α-olefin copolymers)], various esters (for example, polyol esters and dibasic acid esters). And phosphoric acid esters), various ethers (for example, polyphenyl ether), polyglycol, alkylbenzene, alkylnaphthalene, and the like. Of these synthetic oils, polyolefins and polyol esters are particularly preferred from the viewpoints of viscosity characteristics, solubility of additives, and compatibility with seal rubbers.
In this invention, 1 type of the said mineral oil may be used as a base oil, and may be used in combination of 2 or more type. Moreover, the said synthetic oil may be used 1 type and may be used in combination of 2 or more type. Further, one or more mineral oils and one or more synthetic oils may be used in combination.
No particular limitation is imposed on the viscosity of the base oil, varies depending on usage of the lubricating oil composition preferably has a kinematic viscosity of 100 ° C. is 3 to 8 mm 2 / s, kinematic viscosity at 100 ° C. is 3 mm 2 / If it is s or more, the evaporation loss is small. On the other hand, if it is 8 mm 2 / s or less, the power loss due to viscous resistance is small, and the fuel efficiency improvement effect is obtained.
また、基油としては、環分析による％ＣＡが３．０以下で硫黄分の含有量が５０質量ｐｐｍ以下のものが好ましく用いられる。ここで、環分析による％ＣＡとは、環分析（ｎ−ｄ−Ｍ法）にて算出した芳香族分の割合（百分率）を示す。また、硫黄分は、ＪＩＳＫ ２５４１に準拠して測定した値である。
％ＣＡが、３．０以下で、硫黄分が５０質量ｐｐｍ以下の基油は、良好な酸化安定性を有し、酸価の上昇やスラッジの生成を抑制し得ると共に、金属に対する腐食性の少ない潤滑油組成物を提供することができる。より好ましい％ＣＡは１．０以下、さらには、０．５以下であり、またより好ましい硫黄分は３０質量ｐｐｍ以下である。
さらに、基油の粘度指数は、７０以上が好ましく、より好ましくは１００以上、さらに好ましくは１２０以上である。この粘度指数が１２０以上の基油は、温度の変化による粘度変化が小さく、低い温度においても燃費改善効果が得られる。
Further, as the base oil, those having a% CA of 3.0 or less by ring analysis and a sulfur content of 50 mass ppm or less are preferably used. Here,% CA by ring analysis indicates a ratio (percentage) of an aromatic component calculated by ring analysis (ndM method). Moreover, a sulfur content is the value measured based on JISK2541.
A base oil having a% CA of 3.0 or less and a sulfur content of 50 mass ppm or less has good oxidation stability, can suppress an increase in acid value and generation of sludge, and is corrosive to metals. Less lubricating oil composition can be provided. More preferable% CA is 1.0 or less, and further 0.5 or less, and a more preferable sulfur content is 30 ppm by mass or less.
Furthermore, the viscosity index of the base oil is preferably 70 or more, more preferably 100 or more, and still more preferably 120 or more. The base oil having a viscosity index of 120 or more has a small change in viscosity due to a change in temperature, and a fuel efficiency improvement effect can be obtained even at a low temperature.
〔（Ａ）成分〕
本発明で用いる（Ａ）成分は、アルケニル若しくはアルキルコハク酸イミド単体とそのホウ素化物との混合物である。コハク酸イミド単体だけを用いたのでは、高温清浄性とフッ素ゴムシールへの適合性の双方を満足することはできない。
また、（Ａ）成分は、（Ａ−１）アルケニル若しくはアルキルコハク酸モノイミド構造および（Ａ−２）アルケニル若しくはアルキルコハク酸ビスイミド構造を含んでいる。ここで、（Ａ−１）構造としては、アルケニル若しくはアルキルコハク酸モノイミド単体にもとづく構造と、アルケニル若しくはアルキルコハク酸モノイミドモノイミドのホウ素化物に基づく構造の双方が含まれる。（Ａ−２）構造についても同様である。
（Ａ−１）構造としてのアルケニル若しくはアルキルコハク酸モノイミドとしては、例えば、下記式（１）で示されるアルケニル若しくはアルキルコハク酸モノイミドが挙げられる。また、（Ａ−２）構造としてのアルケニル若しくはアルキルコハク酸ビスイミドとしては、例えば、下記式（２）で示されるアルケニル若しくはアルキルコハク酸ビスイミドが挙げられる。
[Component (A)]
The component (A) used in the present invention is a mixture of an alkenyl or alkyl succinimide and a boride thereof. Using only succinimide alone cannot satisfy both high temperature cleanliness and compatibility with fluororubber seals.
The component (A) includes (A-1) an alkenyl or alkyl succinic acid monoimide structure and (A-2) an alkenyl or alkyl succinic acid bisimide structure. Here, the (A-1) structure includes both a structure based on a single alkenyl or alkyl succinic acid monoimide and a structure based on a boride of alkenyl or alkyl succinic monoimide monoimide. The same applies to the structure (A-2).
(A-1) As an alkenyl or alkyl succinic acid monoimide as a structure, the alkenyl or alkyl succinic acid monoimide shown by following formula (1) is mentioned, for example. Moreover, as an alkenyl or alkyl succinic acid bisimide as a structure (A-2), the alkenyl or alkyl succinic acid bisimide shown by following formula (2) is mentioned, for example.
上記式（１）および式（２)において、Ｒ１、Ｒ３およびＲ４は、アルケニル基若しくはアルキル基であり、質量平均分子量は、それぞれ、好ましくは５００〜３，０００、より好ましくは１，０００〜３，０００である。
上記したＲ１、Ｒ３およびＲ４の質量平均分子量が５００未満であると、基油への溶解性が低下し、３，０００を超えると、清浄性が低下するおそれがある。Ｒ３およびＲ４は同一でも異なっていてもよい。
Ｒ２、Ｒ５およびＲ６は、それぞれ炭素数２〜５のアルキレン基であり、Ｒ５およびＲ６は同一でも異なっていてもよい。ｍは１〜１０の整数を示し、ｎは０または１〜１０の整数を示す。ここで、mは、好ましくは２〜５、より好ましくは３〜４である。ｍが２以上であると、良好な高温清浄性を与え、ｍが５以下であると、基油に対する溶解性が良好となる。
上記式（２）において、ｎは好ましくは１〜４であり、より好ましくは２〜３である。モノイミドと異なり、ｎが１以上であれば高温清浄性が良好であり、ｎが４以下であると、基油に対する溶解性が良好となる。
In the above formula (1) and (2), R 1, R 3 and R 4 is an alkenyl group or an alkyl group, the weight average molecular weight, respectively, preferably 500 to 3,000, more preferably 1, 000 to 3,000.
When the mass average molecular weight of R 1 , R 3 and R 4 is less than 500, the solubility in the base oil is lowered, and when it exceeds 3,000, the cleanliness may be lowered. R 3 and R 4 may be the same or different.
R 2 , R 5 and R 6 are each an alkylene group having 2 to 5 carbon atoms, and R 5 and R 6 may be the same or different. m represents an integer of 1 to 10, and n represents 0 or an integer of 1 to 10. Here, m is preferably 2 to 5, more preferably 3 to 4. When m is 2 or more, good high-temperature cleanability is imparted, and when m is 5 or less, solubility in base oil is good.
In said formula (2), n becomes like this. Preferably it is 1-4, More preferably, it is 2-3. Unlike monoimide, if n is 1 or more, high-temperature cleanability is good, and if n is 4 or less, solubility in base oil is good.
アルケニル基としては、例えば、ポリブテニル基、ポリイソブテニル基、エチレン− プロピレン共重合体を挙げることができ、アルキル基としてはこれらを水添したものが挙げられる。好適なアルケニル基としては、ポリブテニル基またはポリイソブテニル基が挙げられる。ポリブテニル基は、１−ブテンとイソブテンの混合物あるいは高純度のイソブテンを重合させたものとして好適に得られる。また、好適なアルキル基の代表例としては、ポリブテニル基またはポリイソブテニル基を水添したものが挙げられる。 Examples of the alkenyl group include a polybutenyl group, a polyisobutenyl group, and an ethylene-propylene copolymer, and examples of the alkyl group include those obtained by hydrogenation thereof. Suitable alkenyl groups include polybutenyl or polyisobutenyl groups. The polybutenyl group is suitably obtained as a mixture of 1-butene and isobutene or a polymer of high-purity isobutene. A representative example of a suitable alkyl group is a hydrogenated polybutenyl group or polyisobutenyl group.
上記のアルケニル若しくはアルキルコハク酸イミドは、通常、ポリオレフィンと無水マレイン酸との反応で得られるアルケニルコハク酸無水物、またはそれを水添して得られる
ルキルコハク酸無水物を、ポリアミンと反応させることによって製造することができる。
また、上記したコハク酸モノイミドおよびコハク酸ビスイミドは、アルケニルコハク酸無水物若しくはアルキルコハク酸無水物とポリアミンとの反応比率を変えることによって製造することができる。
上記したポリオレフィンを形成するオレフィン単量体としては、炭素数２〜８のα−オレフィンの１種または２種以上を混合して用いることができるが、イソブテンとブテン−１の混合物を好適に用いることができる。
一方、ポリアミンとしては、エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ペンチレンジアミン等の単一ジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ジ（メチルエチレン）トリアミン、ジブチレントリアミン、トリブチレンテトラミン、およびペンタペンチレンヘキサミン等のポリアルキレンポリアミンを挙げることができる。
The above alkenyl or alkyl succinimide is usually obtained by reacting an alkenyl succinic anhydride obtained by reaction of a polyolefin with maleic anhydride, or a rualkyl succinic anhydride obtained by hydrogenating it with a polyamine. Can be manufactured.
The succinic monoimide and succinic bisimide described above can be produced by changing the reaction ratio of alkenyl succinic anhydride or alkyl succinic anhydride and polyamine.
As the olefin monomer that forms the above-mentioned polyolefin, one or more of α-olefins having 2 to 8 carbon atoms can be mixed and used, but a mixture of isobutene and butene-1 is preferably used. be able to.
On the other hand, polyamines include single diamines such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di (methylethylene) triamine, dibutylenetriamine, triethylene. Mention may be made of polyalkylene polyamines such as butylenetetramine and pentapentylenehexamine.
また、アルケニル若しくはアルキルコハク酸イミドのホウ素化物は、常法により製造したものを使用することができる。
例えば、上記のポリオレフィンを無水マレイン酸と反応させてアルケニルコハク酸無水物とした後、更に上記のポリアミンと酸化ホウ素、ハロゲン化ホウ素、ホウ酸、ホウ酸無水物、ホウ酸エステル、ホウ素酸のアンモニウム塩等のホウ素化合物を反応させて得られる中間体と反応させてイミド化させることによって得られる。
Moreover, what was manufactured by the conventional method can be used for the boride of an alkenyl or alkyl succinimide.
For example, after reacting the above polyolefin with maleic anhydride to form alkenyl succinic anhydride, the above polyamine and boron oxide, boron halide, boric acid, boric anhydride, boric acid ester, ammonium boric acid It is obtained by reacting with an intermediate obtained by reacting a boron compound such as a salt and imidizing.
ここで、本発明における（Ａ）成分は、前記（Ａ−１）構造に由来する窒素と、前記（Ａ−２）構造に由来する窒素との質量比（（Ａ−１）／（Ａ−２））が０．５以下であり、好ましくは０．４以下である。
質量比（（Ａ−１）／（Ａ−２））が０．５以下であると、フッ素ゴムシールへの適合性を大幅に向上させることができる。質量比（（Ａ−１）／（Ａ−２））が０．５より大きいとフッ素ゴムの劣化が著しくなり、シール寿命が短くなる。
Here, the component (A) in the present invention is a mass ratio ((A-1) / (A-) of nitrogen derived from the structure (A-1) and nitrogen derived from the structure (A-2). 2)) is 0.5 or less, preferably 0.4 or less.
When the mass ratio ((A-1) / (A-2)) is 0.5 or less, compatibility with the fluororubber seal can be greatly improved. When the mass ratio ((A-1) / (A-2)) is larger than 0.5, the fluororubber is significantly deteriorated and the seal life is shortened.
また、本発明の（Ａ）成分におけるアルケニル若しくはアルキルコハク酸イミドホウ素化物を構成するホウ素（Ｂ）と窒素（Ｎ）の質量比（Ｂ／Ｎ比）は、０．５以上であり、好ましくは０．６以上、さらに好ましくは０．８以上である。Ｂ／Ｎ比が０．５以上であると、高温清浄性が大きく向上する。 Further, the mass ratio (B / N ratio) of boron (B) and nitrogen (N) constituting the alkenyl or alkyl succinimide boride in the component (A) of the present invention is 0.5 or more, preferably 0.6 or more, more preferably 0.8 or more. When the B / N ratio is 0.5 or more, the high-temperature cleanability is greatly improved.
（Ａ）成分におけるアルケニル若しくはアルキルコハク酸イミドホウ素化物に由来するホウ素含有量は、組成物全量基準において０．０２〜０．０５質量％である。（Ａ）成分に含まれるホウ素が一定量以上存在することで、高温清浄性が発揮される。ホウ素含有量が、０．０２質量％未満では、十分な高温清浄性は得られない。また、ホウ素含有量が０．０５質量％を超えても高温清浄性についてさらなる向上が図れず、実用性に乏しい。 The boron content derived from the alkenyl or alkyl succinimide boride in the component (A) is 0.02 to 0.05 mass% based on the total amount of the composition. (A) The high temperature detergency is exhibited because the boron contained in the component is present in a certain amount or more. If the boron content is less than 0.02% by mass, sufficient high-temperature cleanability cannot be obtained. Moreover, even if boron content exceeds 0.05 mass%, further improvement is not achieved about high temperature cleanliness, and it is lacking in practicality.
〔（Ｂ）成分〕
本組成物には、さらに（Ｂ）成分として、モリブデンジチオカーバメート（以下、「ＭｏＤＴＣ」とも記載する。）が好ましく配合される。（Ｂ）成分としては、例えば、下記式（３）で示されるＭｏＤＴＣが挙げられる。
[(B) component]
The composition further preferably contains molybdenum dithiocarbamate (hereinafter also referred to as “MoDTC”) as component (B). (B) As a component, MoDTC shown by following formula (3) is mentioned, for example.
ここで、上記式（３）において、Ｒ７〜Ｒ１０は、好ましくは炭素数４〜２２の炭化水素基であり、例えば、アルキル基、アルケニル基、アルキルアリール基、シクロアルキル基、シクロアルケニル基等である。これらの中でも、Ｒ７〜Ｒ１０は炭素数４〜１８の分枝鎖または直鎖のアルキル基またはアルケニル基が好ましく、炭素数８〜１３のアルキル基がより好ましい。例えば、ｎ−オクチル基、２−エチルヘキシル基、イソノニル基、ｎ−デシル基、イソデシル基、ドデシル基、トリデシル基、イソトリデシル基等が挙げられる。これは、あまり炭素数が少ないと基油に対する溶解性に乏しくなるためであり、あまりに炭素数が多くなると融点が高くなりハンドリング性が悪くなるとともに活性も低くなるためである。また、Ｒ７〜Ｒ１０は、互いに同一であってもよいし、異なっていてもよいが、Ｒ７およびＲ８と、Ｒ９およびＲ１０が異なるアルキル基であると、基油への溶解性、貯蔵安定性および摩擦低減能の持続性が向上する。
また、上記式（３）においては、Ｘ１〜Ｘ４は各々硫黄原子または酸素原子であり、Ｘ１〜Ｘ４の全てが硫黄原子あるいは酸素原子であってもよい。ここで、硫黄原子と酸素原子の比が、硫黄原子／酸素原子＝１／３〜３／１、更には１．５／２．５〜３／１であることが耐腐食性の面や、基油に対する溶解性を向上させる上で好ましい。
Here, in the above formula (3), R 7 to R 10 are preferably hydrocarbon groups having 4 to 22 carbon atoms, such as an alkyl group, an alkenyl group, an alkylaryl group, a cycloalkyl group, and a cycloalkenyl group. Etc. Among these, R 7 to R 10 are preferably a branched or straight chain alkyl group or alkenyl group having 4 to 18 carbon atoms, and more preferably an alkyl group having 8 to 13 carbon atoms. For example, n-octyl group, 2-ethylhexyl group, isononyl group, n-decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group and the like can be mentioned. This is because if the number of carbons is too small, the solubility in the base oil becomes poor, and if the number of carbons is too large, the melting point becomes high, handling properties become poor and the activity becomes low. R 7 to R 10 may be the same as or different from each other, but when R 7 and R 8 and R 9 and R 10 are different alkyl groups, they are dissolved in the base oil. , Storage stability and durability of friction reduction ability are improved.
In the above formula (3), X 1 to X 4 may each be a sulfur atom or an oxygen atom, and all of X 1 to X 4 may be a sulfur atom or an oxygen atom. Here, the ratio of sulfur atom and oxygen atom is sulfur atom / oxygen atom = 1/3 to 3/1, and more preferably 1.5 / 2.5 to 3/1, in terms of corrosion resistance, It is preferable for improving the solubility in the base oil.
本発明においては当該（Ｂ）成分は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
また、潤滑油組成物中の当該（Ｂ）成分の配合量は、組成物全量基準におけるモリブデン量換算で０．０１〜０．０８質量％であり、好ましくは０．０３〜０．０８質量％となるように調製される。０．０１質量％を下回ると、十分な摩擦低減効果が得られず、０．０８質量％を上回ると、基油への溶解性および金属材料への腐食性が高くなる。
In this invention, the said (B) component may be used individually by 1 type, and may be used in combination of 2 or more type.
Moreover, the compounding quantity of the said (B) component in a lubricating oil composition is 0.01-0.08 mass% in conversion of the molybdenum amount in a composition whole quantity basis, Preferably it is 0.03-0.08 mass%. To be prepared. If the amount is less than 0.01% by mass, a sufficient friction reducing effect cannot be obtained. If the amount exceeds 0.08% by mass, the solubility in the base oil and the corrosiveness to the metal material are increased.
〔（Ｃ）成分〕
本組成物には、さらに（Ｃ）成分として、ジアルキルジチオリン酸亜鉛（以下、「ＺｎＤＴＰ」とも記載する。）が好ましく配合される。（Ｃ）成分としては、例えば、下記式（４）で示されるＺｎＤＴＰが挙げられる。
[Component (C)]
The composition further preferably contains zinc dialkyldithiophosphate (hereinafter also referred to as “ZnDTP”) as component (C). (C) As a component, ZnDTP shown by following formula (4) is mentioned, for example.
上記式（４）において、Ｒ１１、Ｒ１２、Ｒ１３およびＲ１４は、炭素数３〜２２の第１級または第２級のアルキル基または炭素数３〜１８のアルキル基で置換されたアルキルアリール基から選ばれた置換基であり、それらは互いに同一であってもよいし、異なっていてもよい。 In the above formula (4), R 11 , R 12 , R 13 and R 14 are alkyl substituted with a primary or secondary alkyl group having 3 to 22 carbon atoms or an alkyl group having 3 to 18 carbon atoms. It is a substituent selected from an aryl group, and they may be the same as or different from each other.
本発明においては、これらのＺｎＤＴＰは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよいが、特に、第２級のアルキル基のジチオリン酸亜鉛を主成分とするものが、耐摩耗性を高めるためには好ましい。
ＺｎＤＴＰの具体例としては、ジプロピルジチオリン酸亜鉛、ジブチルジチオリン酸亜鉛、ジペンチルジチオリン酸亜鉛、ジヘキシルジチオリン酸亜鉛、ジイソペンチルジチオリン酸亜鉛、ジエチルヘキシルジチオリン酸亜鉛、ジオクチルジチオリン酸亜鉛、ジノニルジチオリン酸亜鉛、ジデシルジチオリン酸亜鉛、ジドデシルジチオリン酸亜鉛、ジプロピルフェニルジチオリン酸亜鉛、ジペンチルフェニルジチオリン酸亜鉛、ジプロピルメチルフェニルジチオリン酸亜鉛、ジノニルフェニルジチオリン酸亜鉛、ジドデシルフェニルジチオリン酸亜鉛、ジドデシルフェニルジチオリン酸亜鉛等が挙げられる。
In the present invention, these ZnDTPs may be used singly or in combination of two or more, and in particular, those having a secondary alkyl group zinc dithiophosphate as a main component. In order to improve wear resistance, it is preferable.
Specific examples of ZnDTP include zinc dipropyldithiophosphate, zinc dibutyldithiophosphate, zinc dipentyldithiophosphate, zinc dihexyldithiophosphate, zinc diisopentyldithiophosphate, zinc diethylhexyldithiophosphate, zinc dioctyldithiophosphate, dinonyldithiophosphate. Zinc, zinc didecyl dithiophosphate, zinc didodecyl dithiophosphate, zinc dipropylphenyl dithiophosphate, zinc dipentylphenyl dithiophosphate, zinc dipropylmethylphenyl dithiophosphate, zinc dinonylphenyl dithiophosphate, zinc didodecylphenyl dithiophosphate, di Examples include zinc dodecylphenyl dithiophosphate.
本発明の潤滑油組成物においては、前記（Ｃ）成分であるＺｎＤＴＰの配合量は、組成物全量基準におけるリン量換算で０．０７〜０．０９質量％である。本組成物においては、リン量が０．０７質量％未満では耐摩耗性が十分でなく、（Ｂ）成分のＭｏＤＴＣによる摩擦低減効果も十分に発現されない。一方、リン量が０．０９質量％を超えると、排出ガスの浄化触媒への被毒が著しくなって好ましくない。 In the lubricating oil composition of the present invention, the blending amount of ZnDTP as the component (C) is 0.07 to 0.09% by mass in terms of phosphorus amount based on the total amount of the composition. In this composition, when the amount of phosphorus is less than 0.07% by mass, the wear resistance is not sufficient, and the friction reducing effect by the MoDTC of the component (B) is not sufficiently exhibited. On the other hand, if the amount of phosphorus exceeds 0.09% by mass, poisoning of the exhaust gas to the purification catalyst becomes remarkable, which is not preferable.
〔（Ｄ）成分〕
本組成物には、さらに、（Ｄ）成分として、多価アルコールモノ脂肪酸エステルのホウ素化物を配合することが好ましい。
（Ｄ）成分を構成するための多価アルコールとしては、グリセリン、トリメチロールプロパン、およびペンタエリスリトール等が挙げられる。脂肪酸としては、例えば、炭素数８〜２２の飽和または不飽和の脂肪酸が挙げられる。このような脂肪酸としては、例えば、ナタネ油、綿実油、大豆油、ラードおよび牛脂等の動植物油脂から得られたものが好適である。この中で特にグリセリンモノオレエートが金属間の摩擦係数の低減効果が大きく、省燃費性向上の点で好ましい。
[Component (D)]
It is preferable that the composition further contains a borated product of a polyhydric alcohol mono fatty acid ester as the component (D).
(D) As a polyhydric alcohol for comprising a component, glycerol, a trimethylol propane, a pentaerythritol, etc. are mentioned. Examples of the fatty acid include saturated or unsaturated fatty acids having 8 to 22 carbon atoms. As such a fatty acid, for example, those obtained from animal and vegetable oils and fats such as rapeseed oil, cottonseed oil, soybean oil, lard and beef tallow are suitable. Among these, glycerin monooleate is particularly preferable because it has a large effect of reducing the coefficient of friction between metals, and improves fuel efficiency.
多価アルコールモノ脂肪酸エステルのホウ素化物は、以下のような方法によって得ることができる。ここでは、多価アルコールとしてグリセリンを用いた場合を示す。
（１）グリセリンモノ脂肪酸エステル、グリセリンおよびホウ酸を１００〜２３０℃の温度で反応させる方法。
（２）グリセリンとホウ酸を反応させた後、脂肪酸、脂肪酸の低級アルコールエステルおよび脂肪酸ハライドのいずれかと反応させる方法。
（３）グリセリンモノ脂肪酸エステル、脂肪酸およびホウ酸を混合し、約２４０〜２８０℃の温度で反応させる方法。
The borated product of polyhydric alcohol mono fatty acid ester can be obtained by the following method. Here, the case where glycerin is used as a polyhydric alcohol is shown.
(1) A method of reacting glycerin monofatty acid ester, glycerin and boric acid at a temperature of 100 to 230 ° C.
(2) A method in which glycerin and boric acid are reacted and then reacted with any one of fatty acids, fatty acid lower alcohol esters and fatty acid halides.
(3) A method in which glycerin monofatty acid ester, fatty acid and boric acid are mixed and reacted at a temperature of about 240 to 280 ° C.
本組成物において、（Ｄ）成分は、組成物全量基準で０．１〜１質量％配合してなることが好ましく、より好ましくは０．２〜０．６質量％である。
本組成物における（Ｄ）成分の配合量が０．１質量％以上であると、フッ素ゴムへの侵食性をより低減することができる。ただし、（Ｄ）成分の配合量が１質量％を超えてもあまり前記の効果は向上しない上に酸化安定性に悪影響を与える。
In the present composition, the component (D) is preferably blended in an amount of 0.1 to 1% by mass, more preferably 0.2 to 0.6% by mass, based on the total amount of the composition.
When the blending amount of the component (D) in the present composition is 0.1% by mass or more, the erodibility to the fluororubber can be further reduced. However, even if the blending amount of the component (D) exceeds 1% by mass, the above effect is not improved so much and the oxidation stability is adversely affected.
本組成物には、さらに、フェノール系やアミン系などの酸化防止剤を添加することが好ましい。
フェノール系酸化防止剤としては、例えば、オクタデシル−３−（３，５−ジ−tert―ブチルー４−ヒドロキシフェニル）プロピオネート、４，４’−メチレンビス（２，６−ジ−ｔ−ブチルフェノール）；４，４’−ビス（２，６−ジ−ｔ−ブチルフェノール）；４，４’−ビス（２−メチル−６−ｔ−ブチルフェノール）；２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）；２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）；４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）；４，４’−イソプロピリデンビス（２，６−ジ−ｔ−ブチルフェノール）；２，２’−メチレンビス（４−メチル−６−ノニルフェノール）；２，２’−イソブチリデンビス（４，６−ジメチルフェノール）；２，２’−メチレンビス（４−メチル−６−シクロヘキシルフェノール）；２，６−ジ−ｔ−ブチル−４−メチルフェノール；２，６−ジ−ｔ−ブチル−４−エチルフェノール；２，４−ジメチル−６−ｔ−ブチルフェノール；２，６−ジ−ｔ−アミル−ｐ−クレゾール；２，６−ジ−ｔ−ブチル−４−（Ｎ，Ｎ’−ジメチルアミノメチルフェノール）；４，４’−チオビス（２−メチル−６−ｔ−ブチルフェノール）；４，４’−チオビス（３−メチル−６−ｔ−ブチルフェノール）；２，２’−チオビス（４−メチル−６−ｔ−ブチルフェノール）；ビス（３−メチル−４−ヒドロキシ−５−ｔ−ブチルベンジル）スルフィド；ビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）スルフィド；ｎ−オクチル−３−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルフェニル）プロピオネート、ｎ−オクタデシル−３−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルフェニル）プロピオネート；２，２’−チオ［ジエチル−ビス−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］などが挙げられる。これらの中で、特にビスフェノール系およびエステル基含有フェノール系のものが好適である。
It is preferable to add an antioxidant such as phenol or amine to the composition.
Examples of the phenolic antioxidant include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4′-methylenebis (2,6-di-t-butylphenol); 4 4,4'-bis (2,6-di-t-butylphenol); 4,4'-bis (2-methyl-6-t-butylphenol); 2,2'-methylenebis (4-ethyl-6-t-) 2,2′-methylenebis (4-methyl-6-tert-butylphenol); 4,4′-butylidenebis (3-methyl-6-tert-butylphenol); 4,4′-isopropylidenebis (2, 6-di-t-butylphenol); 2,2′-methylenebis (4-methyl-6-nonylphenol); 2,2′-isobutylidenebis (4,6-dimethylphenol); 2'-methylenebis (4-methyl-6-cyclohexylphenol); 2,6-di-t-butyl-4-methylphenol; 2,6-di-t-butyl-4-ethylphenol; 2,4-dimethyl -6-tert-butylphenol; 2,6-di-tert-amyl-p-cresol; 2,6-di-tert-butyl-4- (N, N'-dimethylaminomethylphenol);4,4'- Thiobis (2-methyl-6-tert-butylphenol); 4,4′-thiobis (3-methyl-6-tert-butylphenol); 2,2′-thiobis (4-methyl-6-tert-butylphenol); bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide; bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide; n-octyl-3- (4-hydroxy-3, 5 Di-t-butylphenyl) propionate, n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate; 2,2′-thio [diethyl-bis-3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] and the like. Among these, bisphenol-based and ester group-containing phenol-based ones are particularly preferable.
また、アミン系酸化防止剤としては、例えばモノオクチルジフェニルアミン；モノノニルジフェニルアミンなどのモノアルキルジフェニルアミン系、４，４’−ジブチルジフェニルアミン；４，４’−ジペンチルジフェニルアミン；４，４’−ジヘキシルジフェニルアミン；４，４’−ジヘプチルジフェニルアミン；４，４’−ジオクチルジフェニルアミン；４，４’−ジノニルジフェニルアミンなどのジアルキルジフェニルアミン系、テトラブチルジフェニルアミン；テトラヘキシルジフェニルアミン；テトラオクチルジフェニルアミン；テトラノニルジフェニルアミンなどのポリアルキルジフェニルアミン系、およびナフチルアミン系のもの、具体的にはα−ナフチルアミン；フェニル−α−ナフチルアミン；さらにはブチルフェニル−α−ナフチルアミン；ペンチルフェニル−α−ナフチルアミン；ヘキシルフェニル−α−ナフチルアミン；ヘプチルフェニル−α−ナフチルアミン；オクチルフェニル−α−ナフチルアミン；ノニルフェニル−α−ナフチルアミンなどのアルキル置換フェニル−α−ナフチルアミンなどが挙げられる。これらの中で、ナフチルアミン系よりジフェニルアミン系の方が、酸化防止効果の点から好ましい。 Examples of the amine antioxidant include monooctyl diphenylamine; monoalkyl diphenylamines such as monononyl diphenylamine; 4,4′-dibutyldiphenylamine; 4,4′-dipentyldiphenylamine; 4,4′-dihexyldiphenylamine; 4,4′-diheptyldiphenylamine; 4,4′-dioctyldiphenylamine; dialkyldiphenylamines such as 4,4′-dinonyldiphenylamine; tetrabutyldiphenylamine; tetrahexyldiphenylamine; tetraoctyldiphenylamine; polyalkyldiphenylamine such as tetranonyldiphenylamine And naphthylamine-based, specifically α-naphthylamine; phenyl-α-naphthylamine; further butylphenyl-α Naphthylamine; pentylphenyl -α- naphthylamine; hexylphenyl -α- naphthylamine; heptylphenyl -α- naphthylamine; octylphenyl -α- naphthylamine; and alkyl-substituted phenyl -α- naphthylamine, such as nonylphenyl -α- naphthylamine. Among these, the diphenylamine type is more preferable than the naphthylamine type in terms of the antioxidant effect.
また、本発明においては、他の酸化防止剤としてモリブデンアミン系酸化防止剤をさらに添加してもよい。モリブデンアミン系酸化防止剤としては、６価のモリブデン化合物、具体的には三酸化モリブデンおよび／またはモリブデン酸とアミン化合物とを反応させてなるもの、例えば特開２００３−２５２８８７号公報に記載の製造方法で得られる化合物を用いることができる。６価のモリブデン化合物と反応させるアミン化合物としては特に制限されないが、具体的には、モノアミン、ジアミン、ポリアミンおよびアルカノールアミンが挙げられる。より具体的には、メチルアミン、エチルアミン、ジメチルアミン、ジエチルアミン、メチルエチルアミン、メチルプロピルアミン等の炭素数１〜３０のアルキル基（これらのアルキル基は直鎖状でも分枝状でもよい）を有するアルキルアミン；エテニルアミン、プロペニルアミン、ブテニルアミン、オクテニルアミン、およびオレイルアミン等の炭素数２〜３０のアルケニル基（これらのアルケニル基は直鎖状でも分枝状でもよい）を有するアルケニルアミン；メタノールアミン、エタノールアミン、メタノールエタノールアミン、メタノールプロパノールアミン等の炭素数１〜３０のアルカノール基（これらのアルカノール基は直鎖状でも分枝状でもよい）を有するアルカノールアミン；メチレンジアミン、エチレンジアミン、プロピレンジアミン、およびブチレンジアミン等の炭素数１〜３０のアルキレン基を有するアルキレンジアミン；ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等のポリアミン；ウンデシルジエチルアミン、ウンデシルジエタノールアミン、ドデシルジプロパノールアミン、オレイルジエタノールアミン、オレイルプロピレンジアミン、ステアリルテトラエチレンペンタミン等の上記モノアミン、ジアミン、ポリアミンに炭素数８〜２０のアルキル基またはアルケニル基を有する化合物やイミダゾリン等の複素環化合物；これらの化合物のアルキレンオキシド付加物；およびこれらの混合物等が例示できる。また、特公平３−２２４３８号公報および特開２００４−２８６６公報に記載されているコハク酸イミドの硫黄含有モリブデン錯体等が例示できる。
上述した酸化防止剤の配合量は、組成物全量基準で、０．３質量％以上が好ましく０．５質量％以上であることがより好ましい。一方、２質量％を越えると、潤滑油基油に不溶となるおそれがある。従って、酸化防止剤の配合量は、組成物全量基準で０．３〜２質量％の範囲が好ましい。
In the present invention, a molybdenum amine antioxidant may be further added as another antioxidant. As the molybdenum amine antioxidant, a hexavalent molybdenum compound, specifically, a product obtained by reacting molybdenum trioxide and / or molybdic acid with an amine compound, for example, the production described in JP-A No. 2003-252887 The compound obtained by the method can be used. Although it does not restrict | limit especially as an amine compound made to react with a hexavalent molybdenum compound, Specifically, a monoamine, diamine, a polyamine, and an alkanolamine are mentioned. More specifically, it has an alkyl group having 1 to 30 carbon atoms such as methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine, and methylpropylamine (these alkyl groups may be linear or branched). Alkylamines; alkenylamines having 2 to 30 carbon atoms such as ethenylamine, propenylamine, butenylamine, octenylamine, and oleylamine (these alkenyl groups may be linear or branched); methanolamine, ethanolamine , Alkanolamines having 1 to 30 carbon atoms such as methanolethanolamine and methanolpropanolamine (these alkanol groups may be linear or branched); methylenediamine, ethylenediamine, propylene Amines and alkylenediamines having 1 to 30 carbon atoms such as butylenediamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine; undecyldiethylamine, undecyldiethanolamine, dodecyldipropanolamine , Oleyldiethanolamine, oleylpropylenediamine, stearyltetraethylenepentamine and other monoamines, diamines, polyamines having a C8-20 alkyl group or alkenyl group, and heterocyclic compounds such as imidazoline; alkylene oxides of these compounds Additives; and mixtures thereof. Moreover, the sulfur containing molybdenum complex etc. of the succinimide described in Japanese Patent Publication No. 3-22438 and Unexamined-Japanese-Patent No. 2004-2866 can be illustrated.
The amount of the antioxidant described above is preferably 0.3% by mass or more, and more preferably 0.5% by mass or more, based on the total amount of the composition. On the other hand, if it exceeds 2% by mass, it may become insoluble in the lubricating base oil. Therefore, the blending amount of the antioxidant is preferably in the range of 0.3 to 2% by mass based on the total amount of the composition.
本発明の内燃機関用潤滑油組成物には、本発明の効果を損なわない範囲で、必要に応じてさらに他の添加剤、例えば粘度指数向上剤、金属系清浄剤、流動点降下剤、防錆剤、金属不活性化剤、界面活性剤、および消泡剤等を配合してもよい。 The lubricating oil composition for an internal combustion engine of the present invention may further contain other additives such as a viscosity index improver, a metallic detergent, a pour point depressant, an antibacterial agent as necessary, as long as the effects of the present invention are not impaired. You may mix | blend a rusting agent, a metal deactivator, surfactant, an antifoamer, etc.
粘度指数向上剤としては、例えば、ポリメタクリレート、分散型ポリメタクリレート、オレフィン系共重合体（例えば、エチレン−プロピレン共重合体など）、分散型オレフィン系共重合体、スチレン系共重合体（例えば、スチレン−ジエン共重合体、スチレン−イソプレン共重合体など）などが挙げられる。これら粘度指数向上剤の配合量は、配合効果の点から、組成物全量基準で、０．５〜１５質量％程度であり、好ましくは１〜１０質量％である。 As the viscosity index improver, for example, polymethacrylate, dispersed polymethacrylate, olefin copolymer (for example, ethylene-propylene copolymer), dispersed olefin copolymer, styrene copolymer (for example, Styrene-diene copolymer, styrene-isoprene copolymer, etc.). The blending amount of these viscosity index improvers is about 0.5 to 15% by mass, preferably 1 to 10% by mass, based on the total amount of the composition, from the viewpoint of the blending effect.
金属系清浄剤としては、潤滑油に用いられる任意のアルカリ土類金属系清浄剤が使用可能であり、例えば、アルカリ土類金属スルフォネート、アルカリ土類金属フェネート、アルカリ土類金属サリシレートおよびこれらの中から選ばれる２種類以上の混合物等が挙げられる。アルカリ土類金属スルフォネートとしては、分子量３００〜１，５００、好ましくは４００〜７００のアルキル芳香族化合物をスルフォン化することによって得られるアルキル芳香族スルフォン酸のアルカリ土類金属塩、特にマグネシウム塩および／またはカルシウム塩等が挙げられ、中でもカルシウム塩が好ましく用いられる。アルカリ土類金属フェネートとしては、アルキルフェノール、アルキルフェノールサルファイド、アルキルフェノールのマンニッヒ反応物のアルカリ土類金属塩、特にマグネシウム塩および／またはカルシウム塩等が挙げられ、中でもカルシウム塩が特に好ましく用いられる。アルカリ土類金属サリシレートとしては、アルキルサリチル酸のアルカリ土類金属塩、特にマグネシウム塩および／またはカルシウム塩等が挙げられ、中でもカルシウム塩が好ましく用いられる。前記アルカリ土類金属系清浄剤を構成するアルキル基としては、炭素数４〜３０のものが好ましく、より好ましくは６〜１８の直鎖または分枝アルキル基であり、これらは直鎖でも分枝でもよい。これらはまた１級アルキル基、２級アルキル基または３級アルキル基でもよい。また、アルカリ土類金属スルフォネート、アルカリ土類金属フェネートおよびアルカリ土類金属サリシレートとしては、前記のアルキル芳香族スルフォン酸、アルキルフェノール、アルキルフェノールサルファイド、アルキルフェノールのマンニッヒ反応物、アルキルサリチル酸等を直接、マグネシウムおよび／またはカルシウムのアルカリ土類金属の酸化物や水酸化物等のアルカリ土類金属塩基と反応させたり、または一度ナトリウム塩やカリウム塩等のアルカリ金属塩としてからアルカリ土類金属塩と置換させること等により得られる中性アルカリ土類金属スルフォネート、中性アルカリ土類金属フェネートおよび中性アルカリ土類金属サリシレートだけでなく、中性アルカリ土類金属スルフォネート、中性アルカリ土類金属フェネートおよび中性アルカリ土類金属サリシレートと過剰のアルカリ土類金属塩やアルカリ土類金属塩基を水の存在下で加熱することにより得られる塩基性アルカリ土類金属スルフォネート、塩基性アルカリ土類金属フェネートおよび塩基性アルカリ土類金属サリシレートや、炭酸ガスの存在下で中性アルカリ土類金属スルフォネート、中性アルカリ土類金属フェネートおよび中性アルカリ土類金属サリシレートをアルカリ土類金属の炭酸塩またはホウ酸塩を反応させることにより得られる過塩基性アルカリ土類金属スルフォネート、過塩基性アルカリ土類金属フェネートおよび過塩基性アルカリ土類金属サリシレートも含まれる。 As the metallic detergent, any alkaline earth metal detergent used in lubricating oils can be used, for example, alkaline earth metal sulfonates, alkaline earth metal phenates, alkaline earth metal salicylates, and the like. And a mixture of two or more selected from the above. Alkaline earth metal sulfonates include alkaline earth metal salts of alkyl aromatic sulfonic acids obtained by sulfonated alkyl aromatic compounds having a molecular weight of 300 to 1,500, preferably 400 to 700, particularly magnesium salts and / or Or a calcium salt etc. are mentioned, A calcium salt is used preferably especially. Alkaline earth metal phenates include alkylphenols, alkylphenol sulfides, alkaline earth metal salts of Mannich reactants of alkylphenols, particularly magnesium salts and / or calcium salts, among which calcium salts are particularly preferred. Examples of the alkaline earth metal salicylates include alkaline earth metal salts of alkyl salicylic acid, particularly magnesium salts and / or calcium salts, among which calcium salts are preferably used. The alkyl group constituting the alkaline earth metal detergent is preferably an alkyl group having 4 to 30 carbon atoms, more preferably a linear or branched alkyl group having 6 to 18 carbon atoms, which are linear or branched. But you can. These may also be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups. Further, as the alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate, the above alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, Mannich reaction product of alkylphenol, alkylsalicylic acid, etc. are directly used as magnesium and / or Or it reacts with alkaline earth metal bases such as alkaline earth metal oxides and hydroxides of calcium, or once replaced with alkaline earth metal salts such as sodium salts and potassium salts, etc. Neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earth metal salicylates as well as neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates obtained by Basic alkaline earth metal sulfonates, basic alkaline earth metal sulfonates obtained by heating an alkaline earth metal salicylate and an excess of alkaline earth metal salts or alkaline earth metal bases in the presence of water, Basic alkaline earth metal salicylates or neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates, and neutral alkaline earth metal salicylates in the presence of carbon dioxide. Also included are overbased alkaline earth metal sulfonates, overbased alkaline earth metal phenates, and overbased alkaline earth metal salicylates obtained by reacting.
本発明において金属系清浄剤としては、上記の中性塩、塩基性塩、過塩基性塩およびこれらの混合物等を用いることができ、特に過塩基性サリチレート、過塩基性フェネート、過塩基性スルフォネートの1種以上と中性スルフォネートとの混合がエンジン内部の清浄性、耐摩耗性において好ましい。
金属系清浄剤は、通常、軽質潤滑油基油等で希釈された状態で市販されており、また入手可能であるが、一般的に、その金属含有量が１．０〜２０質量％、好ましくは２．０〜１６質量％のものを用いるのが望ましい。
In the present invention, the above-mentioned neutral salt, basic salt, overbased salt, and a mixture thereof can be used as the metal detergent, and in particular, overbased salicylate, overbased phenate, overbased sulfonate. A mixture of one or more of these and a neutral sulfonate is preferable in terms of cleanliness and wear resistance inside the engine.
Metal-based detergents are usually commercially available in a state diluted with a light lubricating base oil or the like, and are available, but generally the metal content is 1.0 to 20% by mass, preferably Is preferably 2.0 to 16% by mass.
本発明において、金属系清浄剤の全塩基価は、通常１０〜５００ｍｇＫＯＨ／ｇ、好ましくは１５〜４５０ｍｇＫＯＨ／ｇであり、これらの中から選ばれる１種または２種以上併用することができる。なお、ここでいう全塩基価とは、ＪＩＳ Ｋ ２５０１「石油製品および潤滑油−中和価試験方法」の７．に準拠して測定される電位差滴定法（塩基価・過塩素酸法）による全塩基価を意味する。 In the present invention, the total base number of the metal detergent is usually 10 to 500 mgKOH / g, preferably 15 to 450 mgKOH / g, and one or more selected from these can be used in combination. The total base number referred to here is 7. JIS K 2501 “Petroleum products and lubricants—neutralization number test method”. Means the total base number by potentiometric titration method (base number / perchloric acid method) measured according to the above.
また、本発明の金属系清浄剤としては、その金属比に特に制限はなく、通常２０以下のものを１種または２種以上混合して使用できるが、好ましくは、金属比が３以下、より好ましくは１．５以下、特に好ましくは１．２以下の金属系清浄剤を必須成分とすることが、酸化安定性や塩基価維持性および高温清浄性等により優れるため特に好ましい。なお、ここでいう金属比とは、金属系清浄剤における金属元素の価数×金属元素含有量（ｍｏｌ％）／せっけん基含有量（ｍｏｌ％）で表され、金属元素とはカルシウム、マグネシウム等、せっけん基とはスルフォン酸基、フェノール基およびサリチル酸基等を意味する。 Further, the metal detergent of the present invention is not particularly limited in the metal ratio, and usually 20 or less can be used by mixing one or more kinds, but preferably the metal ratio is 3 or less. It is particularly preferable to use a metal-based detergent having an essential component of preferably 1.5 or less, particularly preferably 1.2 or less, because it is excellent in oxidation stability, base number maintenance, high-temperature cleanability and the like. The metal ratio here is represented by the valence of the metal element in the metal-based detergent × metal element content (mol%) / soap group content (mol%), and the metal elements include calcium, magnesium, and the like. The soap group means a sulfonic acid group, a phenol group, a salicylic acid group, and the like.
本発明において、金属系清浄剤の配合量は、組成物全量基準において、金属元素換算量で１質量％以下であり、０．５質量％以下であることが好ましく、さらに組成物の硫酸灰分を０．８質量％以下に低減するためには、０．２質量％以下とするのが好ましい。また、金属系清浄剤の配合量は、金属元素換算量で０．００５質量％以上であることが好ましく、より好ましくは０．０１質量％以上であり、酸化安定性や塩基価維持性、高温清浄性をより高めるために、さらに好ましくは０．０５質量％以上であり、特に０．０８質量％以上とすることでより長期間塩基価および高温清浄性を維持できる組成物を得ることができるため、特に好ましい。なお、ここでいう硫酸灰分とは、ＪＩＳ Ｋ ２２７２の５．「硫酸灰分試験方法」に規定される方法により測定される値を示し、主として金属含有添加剤に起因するものである。 In the present invention, the compounding amount of the metal-based detergent is 1% by mass or less, preferably 0.5% by mass or less in terms of metal element, based on the total amount of the composition, and further the sulfated ash content of the composition. In order to reduce the content to 0.8% by mass or less, the content is preferably 0.2% by mass or less. In addition, the compounding amount of the metallic detergent is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, in terms of metal element, oxidation stability, base number maintenance, high temperature In order to further improve the cleanliness, it is more preferably 0.05% by mass or more, and in particular by 0.08% by mass or more, a composition capable of maintaining the base number and the high temperature cleanliness for a long period of time can be obtained. Therefore, it is particularly preferable. The sulfated ash referred to here is JIS K 2272 5. The value measured by the method prescribed in “Method for testing sulfated ash” is mainly due to the metal-containing additive.
流動点降下剤としては、エチレン−酢酸ビニル共重合体、塩素化パラフィンとナフタレンとの縮合物、塩素化パラフィンとフェノールとの縮合物、ポリメタクリレート、ポリアルキルスチレン等が挙げられ、例えば、質量平均分子量が５，０００〜５０，０００程度のポリメタクリレートが好ましく用いられる。これらは、組成物全量基準で、０．１〜５質量％程度の割合で使用される。
防錆剤としては、石油スルフォネート、アルキルベンゼンスルホネート、ジノニルナフタレンスルホネート、アルケニルコハク酸エステル、多価アルコールエステル等が挙げられる。これら防錆剤の配合量は、配合効果の点から、組成物全量基準で、０．０１〜１質量％程度であり、好ましくは０．０５〜０．５質量％である。
Examples of the pour point depressant include ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, condensate of chlorinated paraffin and phenol, polymethacrylate, polyalkylstyrene, and the like. Polymethacrylate having a molecular weight of about 5,000 to 50,000 is preferably used. These are used at a ratio of about 0.1 to 5% by mass based on the total amount of the composition.
Examples of the rust inhibitor include petroleum sulfonates, alkylbenzene sulfonates, dinonyl naphthalene sulfonates, alkenyl succinic acid esters, and polyhydric alcohol esters. The blending amount of these rust preventives is about 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass, based on the total amount of the composition, from the viewpoint of the blending effect.
金属不活性化剤（銅腐食防止剤）としては、例えば、ベンゾトリアゾール系、トリルトリアゾール系、チアジアゾール系、イミダゾール系およびピリミジン系化合物等が挙げられる。この中でベンゾトリアゾール系化合物が好ましい。金属不活性化剤を配合することでエンジン部品の金属腐食および酸化劣化を抑制することができる。これら金属不活性化剤の配合量は、配合効果の点から、組成物全量基準で、好ましくは０．０１〜０．１質量％、より好ましくは０．０３〜０．０５質量％である。
消泡剤としては、シリコーン油、フルオロシリコーン油およびフルオロアルキルエーテル等が挙げられ、消泡効果および経済性のバランスなどの点から、組成物全量に基づき、０．００５〜０．１質量％程度配合させることが好ましい。
Examples of the metal deactivator (copper corrosion inhibitor) include benzotriazole, tolyltriazole, thiadiazole, imidazole, and pyrimidine compounds. Of these, benzotriazole compounds are preferred. By compounding a metal deactivator, metal corrosion and oxidative deterioration of engine parts can be suppressed. The compounding amount of these metal deactivators is preferably 0.01 to 0.1% by mass, more preferably 0.03 to 0.05% by mass, based on the total amount of the composition, from the viewpoint of the compounding effect.
Examples of antifoaming agents include silicone oils, fluorosilicone oils, fluoroalkyl ethers, and the like. From the viewpoint of balance between defoaming effect and economy, about 0.005 to 0.1% by mass based on the total amount of the composition. It is preferable to mix.
本発明の潤滑油組成物においては、硫黄含有量が組成物全量基準で０．３質量％以下であることが好ましく、０．２質量％以下であることがより好ましく、さらに好ましくは０．１質量％以下である。硫黄含有量が０．３質量％以下であると、排出ガスの浄化触媒の性能低下を効果的に抑えることができる。 In the lubricating oil composition of the present invention, the sulfur content is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.1% by mass or less based on the total amount of the composition. It is below mass%. When the sulfur content is 0.3% by mass or less, the performance deterioration of the exhaust gas purification catalyst can be effectively suppressed.
また、本発明の潤滑油組成物においては、硫酸灰分は０．６質量％以下であることが好ましい。硫酸灰分が０．６質量％以下であると、ディーゼルエンジンにおいて、ＤＰＦのフィルタに堆積する灰分量が少なく、該フィルタの灰分詰まりが抑制され、ＤＰＦの寿命が長くなる。なお、この硫酸灰分とは、試料を燃やして生じた炭化残留物に硫酸を加えて加熱し、恒量にした灰分をいい、通常潤滑油組成物中の金属系添加剤の大略の量を知るために用いられる。具体的には、ＪＩＳ Ｋ ２２７２の「５．硫酸灰分試験方法」に規定される方法により測定される。 In the lubricating oil composition of the present invention, the sulfated ash content is preferably 0.6% by mass or less. When the sulfated ash content is 0.6% by mass or less, in the diesel engine, the amount of ash deposited on the filter of the DPF is small, ash clogging of the filter is suppressed, and the life of the DPF is prolonged. The sulfated ash refers to the ash that is made by adding sulfuric acid to the carbonized residue generated by burning the sample and heating it to make it constant, and is usually used to know the approximate amount of metallic additives in the lubricating oil composition. Used for. Specifically, it is measured by a method defined in “5. Sulfated ash test method” of JIS K 2272.
本発明の内燃機関用潤滑油組成物は、高温清浄性に優れるだけでなく、エンジン内部に多用されるフッ素ゴムシールへの適合性が良好であるので、ガソリンエンジンやディーゼルエンジンなどの内燃機関に好適に用いることができる。 The lubricating oil composition for internal combustion engines of the present invention is not only excellent in high-temperature cleanability, but also has good compatibility with fluorine rubber seals frequently used in the engine, and is therefore suitable for internal combustion engines such as gasoline engines and diesel engines. Can be used.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
〔実施例１、２、比較例１〜５〕
表１に示すように、下記の基油および添加剤を用いて潤滑油組成物（試料油）を調製し、それらの特性・性状を測定するとともに、高温清浄性およびフッ素ゴムシールへの適合性を評価した。
[Examples 1 and 2 and Comparative Examples 1 to 5]
As shown in Table 1, a lubricating oil composition (sample oil) was prepared using the following base oils and additives, their properties and properties were measured, and high temperature cleanliness and compatibility with fluororubber seals were measured. evaluated.
（基油および添加剤）
（１）基油：水素化精製基油、４０℃動粘度２１ｍｍ２／ｓ、１００℃動粘度４．５ｍｍ２／ｓ、粘度指数１２７、％ＣＡ０．１以下、硫黄含有量２０質量ｐｐｍ未満、ＮＯＡＣＫ蒸発量１３．３質量％
（２）ポリブテニルコハク酸ビスイミドＡ：ポリブテニル基の数平均分子量２３００、窒素含有量０．９９質量％、塩素含有量０．０１質量％以下
（３）ポリブテニルコハク酸モノイミドＢ：ポリブテニル基の数平均分子量９８０、窒素含有量２．００質量％、塩素含有量０．０１質量％以下
（４）ポリブテニルコハク酸モノイミドホウ素化物Ｃ：ポリブテニル基の数平均分子量９８０、窒素含有量１．７６質量％、ホウ素含有量２．１質量％、Ｂ／Ｎ比比１．１９、塩素含有量、０．０１質量％以下。
（５）ポリブテニルコハク酸ビスイミドホウ素化物Ｄ：ポリブテニル基の数平均分子量１３００、窒素含有量１．９５質量％、ホウ含有量０．６７質量％、Ｂ／Ｎ比比０．３４、塩素含有量０．０１質量％以下
(Base oil and additives)
(1) Base oil: hydrorefined base oil, 40 ° C. kinematic viscosity 21 mm 2 / s, 100 ° C. kinematic viscosity 4.5 mm 2 / s, viscosity index 127,% CA 0.1 or less, sulfur content less than 20 mass ppm, NOACK evaporation of 13.3 mass%
(2) Polybutenyl succinic acid bisimide A: Number average molecular weight of polybutenyl group 2300, nitrogen content 0.99 mass%, chlorine content 0.01 mass% or less (3) polybutenyl succinic acid monoimide B: polybutenyl group Number average molecular weight 980, nitrogen content 2.00% by mass, chlorine content 0.01% by mass or less (4) polybutenyl succinic acid monoimide borate C: polybutenyl group number average molecular weight 980, nitrogen content 1 0.76 mass%, boron content 2.1 mass%, B / N ratio ratio 1.19, chlorine content, 0.01 mass% or less.
(5) Polybutenyl succinic acid bisimide boride D: number average molecular weight of polybutenyl group 1300, nitrogen content 1.95% by mass, boron content 0.67% by mass, B / N ratio ratio 0.34, chlorine content 0.01 mass% or less
（６）モリブデンジチオカーバメート（ＭｏＤＴＣ）：サクラルーブ５１５（株式会社ＡＤＥＫＡ製）、Ｍｏ含有量１０．０質量％、硫黄含有量１１．５質量％
（７）ジアルキルジチオリン酸亜鉛（ＺｎＤＴＰ）：Ｚｎ含有量９．０質量％、リン含有量８．２質量％、硫黄含有量１７．１質量％、アルキル基；第２級ブチル基と第２級ヘキシル基の混合物
（８）グリセリンのモノオレイン酸エステルのホウ素化物：ホウ素含有量２．２質量％
（９）アミン系酸化防止剤：ジアルキルジフェニルアミン、窒素含有量４．６質量％
（１０）フェノール系酸化防止剤：オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル４−ヒドロキシフェニル）プロピオネート
（１１）粘度指数向上剤：スチレン−イソブチレン共重合体、質量平均分子量５８４，０００、樹脂量１０質量％
（１２）金属系清浄剤Ａ：過塩基性カルシウムフェネート、塩基価（過塩素酸法）２５５ｍｇＫＯＨ／ｇ、カルシウム含有量９．３質量％、硫黄含有量３．０質量％
（１３）金属系清浄剤Ｂ：カルシウムスルホネート、塩基価（過塩素酸法）１７ｍｇＫＯＨ／ｇ、カルシウム含有量２．４質量％、硫黄含有量２．８質量％
（１４）モリブデン系酸化防止剤：サクラルーブＳ−７１０（株式会社ＡＤＥＫＡ製）モリブデン含有量１０質量％
（１５）その他の添加剤：金属不活性化剤、流動点降下剤、消泡剤
(6) Molybdenum dithiocarbamate (MoDTC): SakuraLube 515 (manufactured by ADEKA Corporation), Mo content 10.0% by mass, sulfur content 11.5% by mass
(7) Zinc dialkyldithiophosphate (ZnDTP): Zn content 9.0% by mass, phosphorus content 8.2% by mass, sulfur content 17.1% by mass, alkyl group; secondary butyl group and secondary Mixture of hexyl groups (8) Boride of monooleate of glycerin: boron content 2.2% by mass
(9) Amine-based antioxidant: dialkyldiphenylamine, nitrogen content 4.6% by mass
(10) Phenol-based antioxidant: octadecyl-3- (3,5-di-tert-butyl 4-hydroxyphenyl) propionate (11) Viscosity index improver: styrene-isobutylene copolymer, mass average molecular weight 584,000 , Resin amount 10% by mass
(12) Metal-based detergent A: Overbased calcium phenate, base number (perchloric acid method) 255 mgKOH / g, calcium content 9.3 mass%, sulfur content 3.0 mass%
(13) Metal-based detergent B: calcium sulfonate, base number (perchloric acid method) 17 mg KOH / g, calcium content 2.4 mass%, sulfur content 2.8 mass%
(14) Molybdenum-based antioxidant: SakuraLube S-710 (manufactured by ADEKA Corporation) Molybdenum content 10% by mass
(15) Other additives: metal deactivators, pour point depressants, antifoaming agents
（基油および試料油の特性・性状測定法）
（１）基油および潤滑油組成物の動粘度：
ＪＩＳ Ｋ ２２８３に規定される「石油製品動粘度試験方法」に準拠して測定した。
（２）基油の粘度指数：
ＪＩＳ Ｋ ２２８３に規定される「石油製品動粘度試験方法」に準拠して測定した。
（３）基油の硫黄含有量：
ＪＩＳ Ｋ ２５４１に準拠して測定した。
（４）基油の％ＣＡ：
環分析ｎ−ｄ−Ｍ法にて芳香族成分の割合（百分率）を算出した。
（５）基油のＮＯＡＣＫ蒸発量：
ＪＰＩ−５Ｓ−４１−２００４に準拠して測定した。
（６）ホウ素含有量：
ＪＰＩ−５Ｓ−３８−９２に準拠して測定した。
（７）窒素含有量：
ＪＩＳ Ｋ２６０９に準拠して測定した。
（８）モリブデンおよびリン含有量：
ＪＰＩ−５Ｓ−３８−９２に準拠して測定した。
（９）硫酸灰分：
ＪＩＳ Ｋ２２７２に準拠して測定した。
(Measurement method of characteristics and properties of base oil and sample oil)
(1) Kinematic viscosity of base oil and lubricating oil composition:
It was measured according to “Petroleum product kinematic viscosity test method” defined in JIS K 2283.
(2) Viscosity index of base oil:
It was measured according to “Petroleum product kinematic viscosity test method” defined in JIS K 2283.
(3) Sulfur content of base oil:
The measurement was performed according to JIS K2541.
(4)% CA of base oil:
The ratio (percentage) of the aromatic component was calculated by the ring analysis ndM method.
(5) NOACK evaporation of base oil:
It measured based on JPI-5S-41-2004.
(6) Boron content:
It measured based on JPI-5S-38-92.
(7) Nitrogen content:
The measurement was performed according to JIS K2609.
(8) Molybdenum and phosphorus content:
It measured based on JPI-5S-38-92.
(9) Sulfated ash:
The measurement was performed according to JIS K2272.
（高温清浄性評価法）
高温清浄性は、ＪＰＩ−５Ｓ−５５−９９に準拠してホットチューブ試験で評価した。具体的には、内径２ｍｍのガラス管中に試料油を０．３１ｍＬ／ｈの流量で、空気を１０ｍＬ／ｍｉｎの流量で１６時間流し続けた。ガラス管の温度は３００℃に保った。その後ガラス管中に付着したデポジット付着物の質量を測定した。デポジット付着物の質量が少ないほど高温清浄性に優れている。
(High temperature cleanliness evaluation method)
High temperature cleanliness was evaluated by a hot tube test in accordance with JPI-5S-55-99. Specifically, the sample oil was continuously supplied into a glass tube having an inner diameter of 2 mm at a flow rate of 0.31 mL / h and air at a flow rate of 10 mL / min for 16 hours. The temperature of the glass tube was kept at 300 ° C. Thereafter, the mass of the deposit adhered to the glass tube was measured. The lower the mass of deposit deposit, the better the high temperature cleanability.
（フッ素ゴムシールへの適合性評価法）
フッ素ゴムシールへの適合性は、以下の方法で評価した。フッ素ゴム試験片（ＲＥ１：ＣＥＣ−Ｌ−３９−Ｔ−９６シールゴム適合性試験の試験ゴム材料）を、油温１７０℃で７２時間試料油に浸漬し、浸漬後の試験片について引張試験を行い、クラック発生時のせん断伸張率を測定した。実用上は、せん断伸張率が１５０％以上あることが好ましい。
(Method for evaluating compatibility with fluoro rubber seals)
The conformity to the fluororubber seal was evaluated by the following method. Fluorine rubber test piece (RE1: CEC-L-39-T-96 seal rubber test rubber material test rubber material) is immersed in sample oil for 72 hours at an oil temperature of 170 ° C., and a tensile test is performed on the test piece after immersion. The shear elongation rate at the time of crack generation was measured. Practically, the shear elongation rate is preferably 150% or more.
〔評価結果〕
表１の結果より、本発明の潤滑油組成物を用いた実施例１、２では、ホットチューブ試験におけるデポジット付着量が少ないことから高温清浄性に優れていることがわかる。また、クラック発生時のせん断伸張率が高く、フッ素ゴムシールとの適合性に非常に優れることがわかる。
一方、比較例１および比較例２では、試料油に配合されたポリブテニルコハク酸イミドの、モノイミド／ビスイミド窒素含有量比が１．３５および０．６７と高いため、フッ素ゴムシールとの適合性が不良である。
比較例３では、フッ素ゴムシールとの適合性は良好であるが、試料油に配合されたポリブテニルコハク酸ビスイミドホウ素化物ＤのＢ／Ｎ比が０．３４と低いためホットチューブ試験におけるデポジット付着量が多くなってしまい、高温清浄性が不良であることがわかる。
比較例４および比較例５では、フッ素ゴムシールとの適合性は良好であるが、ポリブテニルコハク酸イミドホウ素化物の配合量が少ないためホットチューブ試験におけるデポジット付着量が多くなり、高温清浄性が不良であることがわかる。
〔Evaluation results〕
From the results of Table 1, it can be seen that in Examples 1 and 2 using the lubricating oil composition of the present invention, the amount of deposit deposited in the hot tube test is small, so that the high temperature cleanliness is excellent. Further, it can be seen that the shear elongation rate at the time of crack occurrence is high, and the compatibility with the fluororubber seal is very excellent.
On the other hand, in Comparative Example 1 and Comparative Example 2, the polybutenyl succinimide compounded in the sample oil has a high monoimide / bisimide nitrogen content ratio of 1.35 and 0.67, so it is compatible with the fluororubber seal. Is bad.
In Comparative Example 3, the compatibility with the fluororubber seal is good, but the B / N ratio of polybutenyl succinic acid bisimide boride D blended in the sample oil is as low as 0.34, so that the deposit in the hot tube test It can be seen that the amount of adhesion increases and the high-temperature cleanliness is poor.
In Comparative Example 4 and Comparative Example 5, the compatibility with the fluororubber seal is good, but since the blending amount of polybutenyl succinimide boride is small, the deposit adhesion amount in the hot tube test is large, and the high temperature cleanliness is high. It turns out that it is bad.
本発明の内燃機関用潤滑油組成物は、ディーゼルエンジンやガソリンエンジンなどの内燃機関に好適に用いられる。 The lubricating oil composition for internal combustion engines of the present invention is suitably used for internal combustion engines such as diesel engines and gasoline engines.
Claims (1)
前記（Ａ）成分は、（Ａ−１）アルケニル若しくはアルキルコハク酸モノイミド構造および（Ａ−２）アルケニル若しくはアルキルコハク酸ビスイミド構造を含み、
前記（Ａ−１）構造に由来する窒素と、前記（Ａ−２）構造に由来する窒素との質量比（（Ａ−１）／（Ａ−２））が０．５以下であり、
前記（Ａ）成分におけるアルケニル若しくはアルキルコハク酸イミドホウ素化物を構成するホウ素と窒素の質量比（Ｂ／Ｎ比）が０．５以上であり、
前記（Ａ）成分におけるアルケニル若しくはアルキルコハク酸イミドホウ素化物に由来するホウ素含有量が組成物全量基準において０．０２〜０．０５質量％であり、
さらに、（Ｂ）モリブデンジチオカーバメートを、組成物全量基準におけるモリブデン量換算で０．０１〜０．０８質量％配合してなり、
さらに、（Ｃ）ジアルキルジチオリン酸亜鉛を、組成物全量基準におけるリン量換算で０．０７〜０．０９質量％配合してなり、
さらに（Ｄ）成分として、多価アルコールモノ脂肪酸エステルのホウ素化物を０．１〜１質量％配合してなり、
該組成物の硫酸灰分が０．６質量％以下である
ことを特徴とする内燃機関用潤滑油組成物。 A lubricating oil composition for an internal combustion engine comprising (A) an alkenyl or alkyl succinimide and a borated product thereof in a base oil,
The component (A) includes (A-1) an alkenyl or alkyl succinic acid monoimide structure and (A-2) an alkenyl or alkyl succinic acid bisimide structure,
The mass ratio ((A-1) / (A-2)) of nitrogen derived from the structure (A-1) and nitrogen derived from the structure (A-2) is 0.5 or less,
The mass ratio (B / N ratio) of boron and nitrogen constituting the alkenyl or alkyl succinimide boride in the component (A) is 0.5 or more,
The boron content derived from the alkenyl or alkyl succinimide boride in the component (A) is 0.02 to 0.05 mass% based on the total amount of the composition,
Furthermore, (B) Molybdenum dithiocarbamate is blended in an amount of 0.01 to 0.08% by mass in terms of molybdenum based on the total amount of the composition,
Further, (C) zinc dialkyldithiophosphate is blended in an amount of 0.07 to 0.09% by mass in terms of phosphorus based on the total amount of the composition,
As a further component (D), Ri polyhydric name a boride alcohol mono fatty acid ester was blended 0.1 to 1 wt%,
A lubricating oil composition for an internal combustion engine, wherein the sulfated ash content of the composition is 0.6% by mass or less .
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